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US8303844B2 - Benzo[f]chrome any pyrano[3,2-f]chrome derivatives for use in liquid crystal media - Google Patents

Benzo[f]chrome any pyrano[3,2-f]chrome derivatives for use in liquid crystal media Download PDF

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US8303844B2
US8303844B2 US12/744,804 US74480408A US8303844B2 US 8303844 B2 US8303844 B2 US 8303844B2 US 74480408 A US74480408 A US 74480408A US 8303844 B2 US8303844 B2 US 8303844B2
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Axel Jansen
Melanie Klasen-Memmer
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • C09K2019/3425—Six-membered ring with oxygen(s) in fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition

Definitions

  • the present invention relates to benzo[f]chromene and pyrano[3,2-f]-chromene derivatives, to a process for the preparation thereof, to liquid-crystalline media comprising these derivatives, and to electro-optical display elements containing these liquid-crystalline media.
  • the invention relates to benzo[f]chromene and pyrano[3,2-f]chromene derivatives having negative dielectric anisotropy.
  • Liquid crystals have found widespread use since the first commercially usable liquid-crystalline compounds were found about 30 years ago.
  • Known areas of application of conventional mixtures are, in particular, displays for watches and pocket calculators, and large display panels as used in railway stations, airports and sports arenas. Further areas of application are displays of portable and desktop computers, navigation systems and video applications. For the last-mentioned applications in particular, high demands are made of the response times and contrast of the images.
  • the spatial arrangement of the molecules in a liquid crystal has the effect that many of its properties are direction-dependent.
  • optical, dielectric and elastomechanical anisotropies are the optical, dielectric and elastomechanical anisotropies.
  • the dielectric constant ⁇ of the liquid-crystalline medium has different values for the two orientations.
  • Substances whose dielectric constant is larger when the longitudinal axes of the molecules are oriented perpendicular to the capacitor plates than when they are oriented parallel are referred to as dielectrically positive.
  • the dipole moment oriented along the longitudinal axis of the molecules is larger than the dipole moment oriented perpendicular to the longitudinal axis of the molecules.
  • a liquid-crystalline layer with a thickness of only from about 5 to 10 ⁇ m is arranged between two plane-parallel glass plates, onto each of which an electrically conductive, transparent layer of tin oxide or indium tin oxide (ITO) has been vapour-deposited as electrode.
  • ITO indium tin oxide
  • a likewise transparent alignment layer usually consisting of a plastic (for example polyimides), is located between these films and the liquid-crystalline layer.
  • This alignment layer serves to bring the longitudinal axes of the adjacent liquid-crystalline molecules into a preferential direction through surface forces in such a way that, in the voltage-free state, they lie uniformly with the same orientation, flat or with the same small tilt angle, on the inside of the display surface.
  • Two polarisation films which only enable linear-polarised light to enter and escape are applied to the outside of the display in a certain arrangement.
  • tricyclic compounds differ from the present invention through the position of the heteroatoms in the rings, the substitution and the degree of saturation of the rings.
  • benzochromene derivatives which are partially unsaturated and optionally have a plurality of heteroatoms are, in addition, disclosed in document WO 2007/079840 A2.
  • they should have negative dielectric anisotropy, which makes them particularly suitable for use in liquid-crystalline media for VA displays.
  • dielectric anisotropy corresponding to the display type
  • compounds are desired which have a favourable combination of the applicational parameters.
  • these parameters which are to be optimised simultaneously, particular mention should be made of a high clearing point, a low rotational viscosity, an optical anisotropy in the use range, and the properties which serve to achieve mixtures having the desired liquid-crystalline phases over a broad temperature range.
  • the compounds have predominantly negative ⁇ and are therefore particularly suitable for use in VA-TFT displays.
  • the compounds according to the invention preferably have a ⁇ of ⁇ 2 and particularly preferably a ⁇ of ⁇ 4. They exhibit very good compatibility with the usual substances used in liquid-crystal mixtures for displays.
  • the compounds of the formula I according to the invention have values for the optical anisotropy ⁇ n which are particularly suitable for use in VA-TFT displays.
  • the compounds according to the invention preferably have a ⁇ n of greater than 0.05 and less than 0.40.
  • the other physical, physicochemical or electro-optical parameters of the compounds according to the invention are also advantageous for use of the compounds in liquid-crystalline media.
  • the compounds or liquid-crystalline media comprising these compounds have, in particular, a sufficient breadth of the nematic phase and good low-temperature and long-term stability as well as sufficiently high clearing points.
  • substituents L 1 and L 2 preference is given to H, F and Cl, in particular H and F. It is furthermore preferred for one or two of the radicals L 1 and L 2 to denote Cl or F, in particular fluorine. L 1 preferably denotes fluorine. L 1 and L 2 particularly preferably denote F.
  • the formula I then also encompasses compounds which may have an overall positive dielectric anisotropy.
  • Such compounds are then suitable for dielectrically positive liquid-crystal mixtures which are used in displays, such as, for example, of the TN-TFT or IPS (‘in-plane switching’) type.
  • the requirements of the other physical parameters, such as, for example, the viscosity are substantially congruent over most applications.
  • the said compounds are thus equally suitable for these purposes since they have favourable values for the parameters, such as rotational viscosity, ⁇ n, etc., and are suitable for the preparation of liquid-crystalline mixtures.
  • a 1 and A 2 are preferably and independently of one another an optionally substituted 1,4-phenylene, an optionally substituted 1,4-cyclohexylene, in which —CH 2 — may be replaced once or twice by —O—, or an optionally substituted 1,4-cyclohexenylene. If n or m is 2, the rings A 1 and A 2 may adopt identical or different meanings.
  • a 1 and A 2 are particularly preferably, independently of one another,
  • a 1 and A 2 are very particularly preferably 1,4-cyclohexylene and/or optionally fluorine-substituted 1,4-phenylene.
  • m+n is equal to 1, and A 1 , A 2 , independently of one another, denote
  • Z 1 and Z 2 are preferably, independently of one another, a single bond, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CF 2 CF 2 —, —CH ⁇ CH—, —CF ⁇ CH—, —CH ⁇ CF— or —CF ⁇ CF—, particularly preferably, independently of one another, a single bond, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 —, —CF 2 CF 2 —, —CH ⁇ CH—, —CF ⁇ CH—, —CH ⁇ CF— or —CF ⁇ CF—.
  • Z 1 and Z 2 are very particularly preferably, independently of one another, a single bond, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 — or —CF ⁇ CF—, in particular a single bond.
  • the parameters m and n in the sum m+n preferably have a value of 0, 1, 2 or 3, particularly 0, 1 or 2.
  • R 1 and R 2 preferably do not denote hydrogen.
  • R 1 and R 2 preferably each, independently of one another, denote an alkanyl radical, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 carbon atoms respectively, where each of these radicals is unsubstituted or mono- or polysubstituted by halogen, or fluorine or hydrogen, particularly preferably an alkanyl radical, alkoxy radical or alkenyl radical as described.
  • R 1 and R 2 in the general formula I are particularly preferably, independently of one another, an alkanyl radical, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 C atoms respectively, where each of these radicals is preferably unsubstituted or mono- or polysubstituted by halogen.
  • R 1 preferably denotes an alkyl or alkoxy group, H or F, particularly preferably an alkyl group having 1-6 C atoms.
  • R 1 and R 2 in the formula I each, independently of one another, represent an alkanyl radical and/or an alkoxy radical (alkyloxy radical) having 1 to 15 C atoms, these are straight-chain or branched.
  • Each of these radicals is preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy.
  • R 1 and R 2 in the formula I may also, independently of one another, be thioalkanyl or sulfonealkanyl radicals, i.e. alkanyl radicals in which one CH 2 group has been replaced by —S— or —SO 2 —.
  • R 1 and R 2 in the formula I may furthermore each, independently of one another, be an alkenyl radical having 2 to 15 C atoms which is straight-chain or branched and has at least one C—C double bond. It is preferably straight-chain and has 2 to 7 C atoms. Accordingly, it is preferably vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, or hept-1-, -2-, -3-, -4-, -5- or -6-enyl. If the two C atoms of the C—C double bond are substituted, the alkenyl radical can be in the form of the E and/or Z isomer (trans/cis). In general, the respective E isomers are preferred.
  • At least one of the CH 2 groups in an alkenyl radical may also have been replaced by oxygen, sulfur or —SO 2 —.
  • oxygen sulfur or —SO 2 —.
  • an alkenyloxy radical having a terminal oxygen
  • an oxaalkenyl radical having a non-terminal oxygen
  • R 1 and R 2 in the formula I may, independently of one another, also be an alkynyl radical having 2 to 15 C atoms which is straight-chain or branched and has at least one C—C triple bond.
  • R 1 and R 2 in the formula I may each, independently of one another, be an alkanyl radical having 1 to 15 C atoms in which one CH 2 group has been replaced by —O— and one has been replaced by —CO—, where these are preferably adjacent. This thus contains an acyloxy group —CO—O— or an oxycarbonyl group —O—CO—.
  • This radical is preferably straight-chain and has 2 to 6 C atoms.
  • R 1 and R 2 in the formula I may each, independently of one another, be an alkenyl radical having 2 to 15 C atoms in which a CH 2 group, preferably in the vicinity of an unsubstituted or substituted —C ⁇ C— unit, has been replaced by —CO—, —CO—O—, —O—CO— or —O—CO—O—, where this radical may be straight-chain or branched.
  • the radical is preferably straight-chain and has 4 to 13 C atoms.
  • acryloyloxymethyl 2-acryloyloxyethyl, 3-acryloyloxypropyl
  • 4-acryloyloxybutyl 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl
  • 4-methacryloyloxybutyl 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl and 8-methacryloyloxyoctyl.
  • a CH 2 group in the vicinity of a substituted unit in —C ⁇ C— unit in an alkynyl radical may also be replaced by —CO—, —CO—O—, —O—CO— or —O—CO—O—.
  • R 1 and R 2 in the formula I may each, independently of one another, be an alkanyl radical or alkoxy radical having 1 to 15 C atoms or an alkenyl radical or alkynyl radical having 2 to 15 C atoms, each of which is monosubstituted by —CN, where these are preferably straight-chain.
  • the substitution by —CN is possible in any desired position.
  • R 1 and R 2 in the formula I may each, independently of one another, be an alkanyl radical in which two or more CH 2 groups have been replaced by —O— and/or —CO—O—, where this may be straight-chain or branched. It is preferably branched and has 3 to 12 C atoms.
  • R 1 and R 2 in the formula I may each, independently of one another, be an alkanyl radical or alkoxy radical having 1 to 15 C atoms or an alkenyl radical or alkynyl radical having 2 to 15 C atoms, each of which is mono- or polysubstituted by F, Cl and/or Br, where these radicals are preferably straight-chain and halogen is preferably —F and/or —Cl. In the case of polysubstitution, halogen is preferably —F.
  • the resultant radicals also include perfluorinated radicals, such as —CF 3 .
  • the fluorine or chlorine substituent can be in any desired position, but is preferably in the ⁇ -position.
  • R 1 and R 2 in the formula I may also each, independently of one another, be —F, —Cl, —Br, —CN, —SCN, —NCS or —SF 5 .
  • the dielectric anisotropy increases towards more positive values.
  • these substituents should not be selected. However, they are preferred for high ⁇ .
  • halogen denotes fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.
  • alkyl unless defined otherwise elsewhere in this description or in the claims—denotes a straight-chain or branched aliphatic hydrocarbon radical having 1 to 15 (i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) carbon atoms. If this alkyl radical is a saturated radical, it is also referred to as “alkanyl”.
  • R 1 , R 2 , A 1 , A 2 , L 1 , L 2 , m, n, Z 1 and Z 2 have the same and the same preferred meanings as defined above for formula I.
  • a 1 and A 2 or Z 1 and Z 2 occur twice in the formulae IA to IF, they can in each case have identical or different meanings.
  • R 1 , R 2 preferably denote an alkyl or alkoxy radical having up to 8 C atoms.
  • index p in the formulae above and below occurs more than once, it can on each occurrence in each case have identical or different meanings, preferably 0, 1 or 2.
  • R 1 and R 2 have the same meanings as defined above.
  • R 1 and R 2 have the same meanings as defined above.
  • R 1 and R 2 preferably denote an alkyl or alkoxy radical having up to 8 C atoms.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 preferably denote an alkyl or alkoxy radical having up to 8 C atoms.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 preferably denote an alkyl or alkoxy radical having up to 8 C atoms.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 preferably denote an alkyl or alkoxy radical having up to 8 C atoms.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 and p have the same meanings as defined above.
  • R 1 , R 2 preferably denote an alkyl or alkoxy radical having up to 8 C atoms.
  • R 1 and R 2 have the same meanings as defined above.
  • R 1 and R 2 have the same meanings as defined above.
  • radicals or substituents of the compounds according to the invention or the compounds according to the invention themselves are in the form of optically active or stereoisomeric radicals, substituents or compounds since they have, for example, a centre of asymmetry, these are likewise encompassed by the present invention.
  • the compounds of the general formula I according to the invention may exist in isomerically pure form, for example as pure enantiomers, diastereomers, E or Z isomers, trans or cis isomers, or as a mixture of a plurality of isomers in any desired ratio, for example as a racemate, E/Z isomer mixture or as a cis/trans isomer mixture.
  • liquid-crystalline media in the compounds according to the invention and in the other components of liquid-crystalline media preferably has the trans configuration, i.e. the two substituents are both in the equatorial position in the thermodynamically preferred chair conformation.
  • the compounds of the general formula I can be prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the said reactions. Use can be made here of variants known per se which are not mentioned here in greater detail.
  • the starting materials can also be formed in situ by not isolating them from the reaction mixture, but instead immediately converting them further into the compounds of the general formula I.
  • R 1 , R 2 , A 1 , A 2 , Z 1 , Z 2 and the indices m and n in the following schemes have at least the meanings as for formula I;
  • R 1 and R 2 can optionally also be a derivatisable group selected from OTs (tosylate), OTf (triflate), OMes (mesylate), —B(OH) 2 , —B(O-alkyl) 2 or —B ⁇ (O—C 2-10 -alkylene-O).
  • the substituents R 11 and R 22 likewise have the thus-expanded meaning of R 1 /R 2 .
  • the substituents A 22 and Z 22 are generally defined like the radicals A 2 and Z 2 respectively; the variables in the group —[Z 22 -A 22 ] n -R 22 are selected in such a way that the group together with the closest group between —[Z 22 -A 22 ] n -R 22 and the tricyclic radical corresponds overall to a radical of the formula —[Z 2 -A 2 ] n -R 2 .
  • a group of the formula —CH ⁇ CH—[Z 22 -A 22 ] n -R 22 or also of the formula -Ph-[Z 22 -A 22 ] n -R 22 is intended formally to correspond to a radical of the formula —[Z 2 -A 2 ] n -R 2 .
  • the compounds of the formula I are preferably synthesised starting from the compounds 2 (cf. Scheme I).
  • the compounds 2 are etherified using propargyl alcohols 3 (method A) [O. Mitsunobu, Synthesis 1981, 1] or propargyl bromides 4 (method B) to give the corresponding compounds 5.
  • the propargyl aryl ethers 5 undergo a [3.3]-sigmatropic rearrangement on heating in N,N-diethylaniline to give the chromene derivatives 6 [H. Ishii, T. Ishikawa, S. Takeda, S. Ueki, M. Suzuki, Chem. Pharm. Bull. 1992, 40, 1148-1153].
  • Final hydrogenation then gives the target compounds 1, which correspond to the compounds of the formula I according to the invention or an intermediate for the preparation thereof.
  • Suitable propargyl alcohols 3 or propargyl bromides 4 are either commercially available or can be synthesised by processes which have already been published.
  • ring B in the compounds of the formula I represents a cyclohexyl radical and if L 1 and L 2 are both equal to F, the synthesis of the compounds 2 (or here of the compounds 2a) starts with compound 7, the synthesis of which is disclosed in WO 2004/029015 A1 (cf. Scheme II).
  • the functionalisation of the ⁇ -tetralone 7 starts with the cerium(III) chloride-promoted addition reaction of corresponding Grignard or organolithium compounds (cf. a) N. Takeda, T. Imamoto, Org. Synth. 1999, 76, 228-238. b) M. Scommoda et al. J. Org. Chem. 1996, 61, 4379-4390). Elimination by treatment with mesyl chloride and DBU (cf. M. Scommoda et al. above) gives the compounds 9 as the principal component in the isomer mixture.
  • ring B in the compounds of the formula I according to the invention represents a cyclohexyl radical and if one of the substituents L 1 and/or L 2 is equal to H, the synthesis of the compounds 2 is carried out starting from the compounds 11.
  • L 1 or L 2 in 11 is preferably H, the other substituent is F.
  • the compounds 11 (6-methoxynaphthalen-2-ones) are to this end firstly functionalised by a cerium(III) chloride-promoted addition reaction of corresponding Grignard or organolithium compounds (cf. above).
  • the elimination (cf. above) in turn gives the compounds 13 as the principal components in the isomer mixtures. Hydrogenation thereof gives 6-methoxy-1,2,3,4-tetrahydronaphthalenes 14.
  • the methyl ether is finally cleaved using boron tribromide (cf. a) J. F. W. McOmie, D. E. West, Org. Synth., Coll. Vol. V 1973, 412; b) E. H. Vickery, L. F. Pahler, E. J. Eisenbraun, J. Org. Chem. 1979, 44, 4444-4446).
  • 3-fluoro-4-methoxyphenylacetic acid 15 starting from 2-fluoroanisole has been described by M. Kucha ⁇ hacek over (r) ⁇ et al. ( Collect. Czech. Chem. Commun. 1990, 55, 296-306).
  • 2-Fluoro-4-methoxyphenylacetic acid 16 is obtained from 2-fluoro-4-hydroxyphenylacetic acid [S.-I. Sugita, S. Toda, T. Yoshiyasu, T. Teraji, Mol. Cryst. Liq. Cryst. 1993, 237, 399-406; E. J. Corey, J. P. Dittami, J. Am. Chem. Soc. 1985, 107, 256-257; H. H. Wassermann, J. Wang, J. Org. Chem. 1998, 63, 5581-5586] by dimethylation and ester saponification.
  • a further, particularly preferred synthesis of the compounds 2 starts from compound 17 or compounds 18.
  • the synthesis of 17 is carried out starting from 7 by generation of the enol ether and reaction thereof with trifluoroacetic anhydride.
  • the compounds 18 are prepared analogously from compounds 11 (cf. Scheme V).
  • the enol triflates 17 and 18 can be functionalised in a variety of ways in transition metal-promoted cross-coupling reactions [ Metal - catalyzed Cross - coupling Reactions (Eds.: A. de Meijre, F. Diederich), Wiley-VCH, Weinhelm, 2nd Edn. 2004] (cf. Scheme VI and Scheme IX).
  • Cross couplings with arylboronic acids 19 (Suzuki couplings), alkenylboronic acids 21 and 23 [C. Sun, R. Bittman, J. Org. Chem. 2006, 71, 2200-2202 and A. Torrado, S. Lopez, R. Alvarez, A. R.
  • B in the compounds 1 according to the invention is intended to be a cyclohexenyl radical
  • the compounds 9 are converted into the dihydronaphthols 2c via the reaction sequence of ortho-metallation and hydrolysis and oxidation of the boronic acid ester formed in situ (cf. Scheme VII).
  • B in the compounds 1 according to the invention is intended to be a cyclohexyl radical
  • the compounds 9 are firstly hydrogenated to give the compounds 10 and subsequently converted into the corresponding tetrahydronaphthols 2a as above (cf. Scheme VIII).
  • Scheme IX shows some examples of cross-coupling reactions of the enol triflates 18.
  • ring B in the compounds 2 is intended to represent a cyclohexenyl radical and if L 1 and/or L 2 are intended to be equal to H, a methyl ether cleavage is carried out using the intermediates 13 to give the corresponding starting materials 2d (cf. Scheme X).
  • ring B in the compounds 2 is intended to represent a cyclohexyl radical and if L 1 and/or L 2 are intended to be equal to H or F, a hydrogenation to give the compounds 14 is carried out before the methyl ether cleavage (cf. Scheme XI).
  • R 2 -(A 2 -Z 2 ) n — is intended to represent an alkoxy radical
  • a simple etherification of 33 using alkyl iodides or bromides is carried out (cf. Scheme XIII).
  • R 2 -(A 2 -Z 2 ) n — is intended to represent an alkenyl radical
  • the triflates 34 are reacted with corresponding alkenylboronic acids in a palladium-catalysed cross coupling (cf. a) C. Sun, R. Bittmann, J. Org. Chem. 2006, 71, 2200-2202; b) A. Torrado, S. Lopez, R. Alvarez, A. R. de Lera, Synthesis 1995, 285-293).
  • These alkenyl compounds 37 can then be converted into the corresponding saturated compounds 38 by hydrogenation (cf. Scheme XIV).
  • transition metal-promoted cross couplings of the triflates 34 for example with arylboronic acids (Suzuki coupling), terminal alkynes (Sonogashira coupling) and Grignard reagents (Kumada coupling or iron(III)-promoted cross coupling) (cf. Scheme XV, only functionalisation via coupling to Grignard reagents is shown here, for further functionalisation possibilities cf. Scheme VI or Scheme IX) are particularly preferred methods for obtaining functionalised naphthalene derivatives 39.
  • the tetralones 13 are converted into the corresponding naphthols 40 by treatment with bromine (cf. WO 2004/029015 A1).
  • the triflates 41 obtained from 40 can then be functionalised in a variety of ways as described above for 34 (cf. Scheme XIV and Scheme XV).
  • Scheme XVII shows only the functionalisation of 41 via a Kumada coupling. Further reactions of the triflates 41 are possible, as described above (cf. Scheme VI and Scheme IX). Cleavage of the methyl ether 42 gives the starting materials 2f required for further reactions (cf. Scheme I).
  • R 2 -(A 2 -Z 2 ) n — in 2f is intended to represent an alkoxy radical
  • the synthesis must be modified.
  • methods can be used in the final step of the synthesis of the compounds 7f (cf. Scheme XVII) which allow the cleavage of aryl methyl ethers in the presence of other alkyl aryl ethers (A. K. Chakraborti et al. J. Org. Chem. 2002, 67, 6406-6414; G. Majetich et al. Tetrahedron Lett. 1994, 35, 8727-8730; E. Duran et al.
  • the methyl group of the bromotoluenes 47 is firstly brominated using NBS, and the bromomethylene compounds 48 are converted into the corresponding nitriles using potassium cyanide. These are then hydrolysed to the phenylacetic acids 49, which are then converted into the desired bromotetralones 43.
  • the naphthols 44 are firstly fluorinated using Selecfluor® (F-TEDA-BF 4 ) to give the difluoro-1H-naphthalen-2-ones 50 (cf. WO 2004/029015 A1), which are then reduced to 1H-naphthalen-2-ols 51. These rearomatise on treatment with base to give the compounds 52 with elimination of hydrogen fluoride.
  • the compounds 52 are then also central intermediates for the synthesis of compounds in which R 2 -A 2 -Z 2 is intended to represent an alkoxy radical (Scheme XX, final reaction). To this end, they are firstly etherified using suitable alkyl halides and subsequently converted into the naphthol 2h.
  • 1,2,3,8,9,10-Hexahydropyrano[3,2-f]chromenes, pyranochromans for short are compounds of the formula I in which ring 13 represents an oxygen heterocycle. These compounds are also prepared in accordance with Scheme I from the corresponding compounds 2.
  • ring B in the compounds of the formula I represents an oxygen heterocycle and if L 1 and L 2 are both equal to F, 7,8-difluorochroman-6-ols 2j are required as starting materials. These are synthesised starting from 2,3-difluorophenol (51) or 3,4-difluoro-2-hydroxybenzaldehyde (55) [a) N. J. Lawrence, L. A. Hepworth, D. Rennison, A. T. McGown, J. A. Hadfield, J. Fluorine Chem. 2003, 123, 101-108. b) E. Marzi, J. Gorecka, M. Schlosser, Synthesis 2004, 1609-1618] (cf. Scheme XXII).
  • 2,3-difluorophenol (51) and a propargyl alcohol 52 are firstly reacted by a Mitsonobu etherification to give a propargyl aryl ether 53, which undergoes a thermal [3.3]-sigmatropic rearrangement under suitable reaction conditions to give a 2H-chromene.
  • These chromenes can easily be hydrogenated under mild conditions to give the corresponding chromans 54.
  • these 7,8-difluorochromans 2j are obtained from 3,4-difluoro-2-hydroxybenzaldehyde (55) [a) N. J. Lawrence, L. A. Hepworth, D. Rennison, A. T. McGown, J. A. Hadfield, J. Fluorine Chem. 2003, 123, 101-108; b) E. Marzi, J. Gorecka, M. Schlosser, Synthesis 2004, 1609-1618] via a reaction which has been described by Petasis et al. [a) N. A. Petasis, I. Akritopoulou, Tetrahedron Lett. 1993, 34, 583-586; b) N. A. Petasis, I. A.
  • ring B in the compounds of the formula I represents a pyran ring and if L 1 is equal to F and L 2 is equal to H, the synthesis of the compounds 2 (especially 7-fluorochroman-6-ols 2k) is carried out starting from 5-bromo-4-fluoro-2-hydroxybenzaldehyde (58).
  • This starting material 58 is accessible via literature-known processes from 3-fluorophenol by ortho-selective formylation [J. B. Blair et al., J. Med. Chem. 2000, 43, 4701-4710] and subsequent bromination [W. A. Caroll et al., J. Med. Chem. 2004, 47, 3163-3179].
  • the synthesis of the chromans 60 is in turn advantageously carried out starting from 5-bromo-4-fluoro-2-hydroxybenzaldehyde (58) by the reaction with vinylboronic acids described above [Q. Wang, M. G. Finn, Org. Lett. 2000, 2, 4063-4065] followed by hydrogenation.
  • the functionalisation to give the chromanol 2k is carried out as described above, this time after halogen-metal exchange.
  • ring B in the compounds of the formula I represents a pyran ring and if L 1 is equal to H and L 2 is equal to F, the synthesis of the compounds 2 (especially 8-fluorochroman-6-ols 2l) is carried out starting from 2-fluoro-4-bromophenol (61).
  • the O-heterocycle is preferably fused here by means of a Claisen rearrangement via the propargyl aryl ether 62 (cf. Scheme XXIV).
  • the functionalisation to give the chromanol 2l is carried out using the same reaction sequence as for the regioisomer 2k.
  • the intermediates 2l can also be synthesised starting from 2-fluoro-4-bromophenol (61) via the salicylaldehyde 64 (cf. Scheme XXV). This is accessible from 61 via a Duff reaction [M. L. Micklatcher, M. Cushman, Synthesis 1999, 1878-1880].
  • the subsequent synthesis of the chroman 63 can then be carried out via the procedure described by Wang and Finn [q. Wang, M. G. Finn, Org. Lett. 2000, 2, 4063-4065] followed by hydrogenation.
  • the tricyclic structure is built up regioselectively by two successive Petasis reactions (cf. Scheme XXVI).
  • 2,5-Dihydroxybenzaldehyde (65) is firstly brominated and selectively protected by processes known from the literature [Y. Hu, C. Li, B. A. Kulkarni, G. Strobel, E. Lokovsky, R. M. Torczynski, J. A. Porto, Org. Lett. 2001, 3, 1649-1652].
  • the chroman 67 is obtained by a first Petasis reaction followed by hydrogenation. Halogen-metal exchange, formylation and complete removal of the TBS protecting group gives a substrate 68 for a second Petasis reaction. Final hydrogenation results in the target compounds 1a.
  • the saturated O-heterocycle is then built up starting from the compounds of the formula 71.
  • the compounds 2 are firstly brominated in a suitable manner.
  • the MOM ethers of the substances 2 are firstly prepared. These are metallated selectively in the ortho-position using n-butyllithium, and the organolithium compounds are scavenged using bromine.
  • halogenation can also be carried out directly by treatment with bromine (cf. Scheme XXVII, method B) (cf. a) C. W. Holzapfel, D. B. G. Williams, Tetrahedron 1995, 51, 8555-8564; b) K. J. Edgar, S. N. Falling, J. Org. Chem. 1990, 55, 5287-5291; c) R. Johnsson, A. Meijer, U. Ellervik, Tetrahedron 2005, 61, 11567-11663).
  • Etherification using bromopropanol derivatives 70 gives the compounds 71.
  • the organolithium compound produced from these compounds (method A) or the Grignard reagent produced from these compounds (method B) cyclises spontaneously under the reaction conditions with formation of the compounds 1.
  • Suitable starting materials 2 in which the radical R 2 [A 2 Z 2 ] n — contains unsaturated radicals, bridges or ring systems are for the most part accessible as described above. It is only necessary to modify the syntheses for compounds 2 in which ring B represents a cyclohexyl radical and for compounds in which ring B represents a pyran ring.
  • the present invention also encompasses, in an embodiment, one or more processes for the preparation of the compounds of the formula I.
  • the invention thus encompasses a process for the preparation of the compounds of the formula I which is characterised in that it includes a process step in which a compound of the formula
  • n, A 2 and Z 2 are as defined above for formula I, and
  • R 22 is as defined for R 1 and may additionally denote —OTs, OTf, OMes or —B(OH) 2 , —B(O-alkyl) 2 , —B ⁇ (O—C 2-10 -alkylene-O),
  • the process product is a compound of the formula I or an intermediate which is suitable for the preparation of compounds of the formula I.
  • the compounds of the general formula I can be used in liquid-crystalline media.
  • the present invention therefore also relates to a liquid-crystalline medium comprising at least two liquid-crystalline compounds, comprising at least one compound of the general formula I.
  • the present invention also relates to liquid-crystalline media comprising 2 to 40, preferably 4 to 30, components as further constituents besides one or more compounds of the formula I according to the invention. These media particularly preferably comprise 7 to 25 components besides one or more compounds according to the invention.
  • These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, 1,3-dioxanes, 2,5-tetrahydropyrans, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecar
  • L and E which may be identical or different, each, independently of one another, denote a divalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -Thp-, -G-Phe- and -G-Cyc- and their mirror images, where Phe denotes unsubstituted or fluorine-substituted 1,4-phenylene, Cyc denotes trans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr denotes pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio denotes 1,3-dioxane-2,5-diyl, Thp denotes tetrahydr
  • One of the radicals L and E is preferably Cyc or Phe.
  • E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention preferably comprise one or more components selected from the compounds of the formulae (II), (III), (IV), (V) and (VI) in which L and E are selected from the group consisting of Cyc and Phe and simultaneously one or more components selected from the compounds of the formulae (II), (III), (IV), (V) and (VI) in which one of the radicals L and E is selected from the group consisting of Cyc and Phe and the other radical is selected from the group consisting of -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulae (II), (III), (IV), (V) and (VI) in which the radicals L and E are selected from the group consisting
  • R′ and R′′ each, independently of one another, denote alkyl, alkenyl, alkoxy, alkoxyalkyl (oxaalkyl), alkenyloxy or alkanoyloxy having up to 8 C atoms.
  • This smaller sub-group is called group A below, and the compounds are referred to by the sub-formulae (IIa), (IIIa), (IVa), (Va) and (VIa).
  • R′ and R′′ are different from one another, one of these radicals usually being alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).
  • R′ and R′′ are as defined for the compounds of the sub-formulae (IIa) to (VIa) and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).
  • R′′ denotes —CN.
  • This sub-group is referred to below as group C, and the compounds of this sub-group are correspondingly described by sub-formulae (IIc), (IIIc), (IVc), (Vc) and (VIc).
  • R′ is as defined for the compounds of the sub-formulae (IIa) to (VIa) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).
  • the media according to the invention preferably comprise one or more compounds from groups A, B and/or C.
  • the proportions by weight of the compounds from these groups in the media according to the invention are:
  • the media according to the invention preferably comprise from 1 to 40%, particularly preferably from 5 to 30%, of the compounds of the formula I according to the invention.
  • the media preferably comprise one, two, three, four or five compounds of the formula I according to the invention.
  • n independently of one another, denote 1, 2, 3, 4, 5, 6, 7 or 8.
  • the media according to the invention are prepared in a manner conventional per se.
  • the components are dissolved in one another, preferably at elevated temperature.
  • the liquid-crystalline phases of the present invention can be modified in such a way that they can be used in all types of liquid-crystal display element that have been disclosed hitherto.
  • Additives of this type are known to the person skilled in the art and are described in detail in the literature (H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980).
  • pleochroic dyes can be added for the production of coloured guest-host systems or substances can be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases.
  • the compounds of the formula I are particularly suitable for use in VA-TFT displays.
  • the present invention therefore also relates to electro-optical liquid-crystal display elements containing a liquid-crystalline medium according to the invention.
  • ⁇ n denotes the optical anisotropy (589 nm, 20° C.) and ⁇ denotes the dielectric anisotropy (1 kHz, 20° C.).
  • the dielectric anisotropy ⁇ is determined at 20° C. and 1 kHz.
  • the optical anisotropy ⁇ n is determined at 20° C. and a wavelength of 589.3 nm.
  • ⁇ and ⁇ n values and the rotational viscosity ( ⁇ 1 ) of the compounds according to the invention are obtained by linear extrapolation from liquid-crystalline mixtures consisting of 5 to 10% of the respective compound according to the invention and 90-95% of the commercially available liquid-crystal mixture ZLI-2857 (for ⁇ ) or ZLI-4792 (for ⁇ n, ⁇ 1 ) (mixtures, Merck KGaA, Darmstadt).
  • the starting substances can be obtained in accordance with generally accessible literature procedures or commercially.
  • the crude product is purified by column chromatography (SiO 2 , 1-chlorobutane), giving 5,6-difluoro-8-(4-propylcyclohexyl)-1,2,3,8-tetrahydropyrano[3,2-f]chromene as a pale-brown oil.
  • the further purification is carried out by repeated recrystallisation from n-heptane at 5° C., giving 5,6-difluoro-3-(4-propylcyclohexyl)-1,2,3,8,9,10-hexahydropyrano[3,2-f]chromene as a colourless solid (m.p. 152° C.).
  • the mixture is stirred at RT for 2 h.
  • Water is added, and the batch is acidified using dil. hydrochloric acid.
  • the solution is extracted a number of times with MTBE, and the combined organic phases are washed successively with water, sat. sodium chloride soln. and ammonium iron(II) sulfate soln.
  • the solution is dried using sodium sulfate and evaporated to dryness.
  • the crude product is purified by column chromatography (SiO 2 , toluene).
  • 30.0 g (about 0.1 mol) of 7-ethoxy-1,2-difluoronaphthalene are initially introduced in 300 ml of THF, and 130.0 ml (0.21 mol) of n-BuLi (15% soln. in hexane) are added at ⁇ 75° C.
  • 25.0 ml (0.22 mol) of trimethyl borate are added dropwise, and the batch is warmed to ⁇ 10° C.
  • 50 ml of dilute acetic acid (about 30%) are added, and the mixture is warmed to 30° C.
  • 40 ml of hydrogen peroxide solution (35%) are carefully added, and the mixture is stirred vigorously for 18 h.
  • the further purification is carried out by recrystallisation from n-heptane, giving 8-ethoxy-5,6-difluoro-3-(4-propylcyclohexyl)-3H-benzo[f]chromene as a yellow solid.

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